Electrolytic cells with at least three electrodes



Jan. 21, 1969 E. J. PLEHAL ETAL 3,423,642

ELECTROLYTIC CELLS WITH AT LEAST THREE ELECTRODES Filed Oct. 18, 1966Sheet of 4 EH ll] Jan. 21, 1969 E. J. PLEHAL ETAL 3,423,642

ELECTROLYTIC CELLS WITH AT LEAST THREE ELECTRODES Filed Oct. 18. 1966Sheet 2 of 4 xed 46254 Arrows arr Jan. 21, 1969 E. .1. PLEHAL ETALELECTROLYTIC CELLS WITH AT LEAST THREE ELECTRODES 1969 E. J. PLEHAL.ETAL 3, 23,642

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Filed Oct. 18, 1966 United States Patent 3,423,642 ELECTROLYTIC CELLSWITH AT LEAST THREE ELECTRODES Edward J. Plehal, Woodland Hills, GeneFrick, Pacific Palisades, and Martin Mintz, Woodland Hills, Calif.,assignors to The Bissett-Berman Corporation, Santa Monica, Calif., acorporation of California Filed Oct. 18, 1966, Ser. No. 587,590 US. Cl.317-231 Int. Cl. H01g 9/04 20 Claims ABSTRACT OF THE DISCLOSURE Thisinvention relates to electrolytic cells. The electrolytic cells of thepresent invention are characterized by a pair of electrodes which are incontact with an electrolyte. The electrodes of the electrolytic cell areused to transfer an active material between the electrodes. The activematerial is transferred through the electrolyte by the passage ofelectrical current between the electrodes. For example, one electrodemay be coated with an active material such as silver and the otherelectrode may be coated with a plating surface such as an inertmaterial, such as gold. When electrical current is applied through theelectrolytic cell in the proper direction, the silver from the oneelectrode is electroplated on the gold surface of the other electrode.

The present invention relates to improvements in electrolytic cells ofthe type as described above. Specifically, one aspect of the presentinvention relates to particular structures for electrolytic cells whichinclude more than the minimum number of only two electrodes. Theseelectrolytic cells, therefore, may be generally characterized asmultiple-electrode electrolytic cells. The present invention is alsodirected to new constructions for electrolytic cells which eliminatecostly assembly procedures which are found in prior art electrolyticcells. For example, prior art electrolytic cells require soldering orwelding operations so as to attach electrical leads to the electrodes.The present invention provides for a mechanical attachment of electricalleads such as by the attachment of electrical leads through a crimpingoperation. The mechanical attachment of the electrical leads of thepresent invention is simpler and more reliable than prior art methods ofattachment.

The electrolytic cells of the prior art and of the present invention areused for various timing and integration functions. For example,copending application Ser. No. 179,847, filed Mar. 15, 1962, in the nameof Thomas B. Bissett and assigned to the assignee of the instantapplication, relates to various uses for electrolytic cells. Asindicated above, the electrolytic cells include at least a pair ofelectrodes, both of which are in contact with an electrolyte so 'as totransfer the active material between the electrodes with the passage ofcurrent through the electrolytic cell. It is often desirable to useelectrolytic cells for more than one timing or integration function. Forexample, it may be desirable to provide for two timing functions with asingle electrolytic cell and it would, therefore, be necessary toprovide the single electrolytic cell with a multiple ICC electrodestructure. As indicated above, one aspect of the present invention isthe construction of electrolytic cells having such multiple eelctrodestructures.

One difficulty with prior art electrolytic cells is that they wererelatively expensive to manufacture especially if the electrolytic cellswere of a small size. The present invention is also directed totechniques to reduce the cost of the electrolytic cells whilemaintaining a small size for the electrolytic cells.

One particular structure for an electrolytic cell which has beenproposed in prior applications filed on behalf of applicants assigneeincludes an outer housing member shaped like a can having a closed endand an open end and wherein the outer housing member serves as anelectrode. The outer housing member may be constructed completely of anactive material such as silver or may be constructed of a base metalplated with the active material such as silver. An inner electrode isdisposed within the outer housing member and the inner electrode extendsinto the outer electrode through the open end. The open end of the outerhousing member is physically deformed against an insulator structure soas to provide a seal for the electrolytic cell. The electrolyte is, ofcourse, sealed within the outer electrode so that it is in contact withboth the inner and outer electrodes.

A clearer understanding of the above described prior art type ofelectrolytic cell is shown in copending application Ser. No. 519,634filed Jan. 10, 1966, in the name of Martin Mintz and assigned to theassignee of the instant application. As can be seen in the copendingMintz application, the electrolytic cell may include an enlarged portionof the outer electrode. The inner electrode has a flange member to fitwithin the enlarged portion of the outer electrode and a pair ofinsulating members sandwich the flange member of the inner electrodewithin the enlarged portion of the outer electrode. The end of the outerelectrode is then crimped over to grip one of the insulating members soas to seal the electrolytic cell.

The electrolytic cell shown in the copending Mintz application whereinthe outer housing also serves as an electrode is relatively inexpensiveto manufacture and is relatively small since the outer housing providesfor two functions. One aspect of the present invention is directed toimprovements in the electrolytic cell of the type described in thecopending Mintz application wherein all electrical leads which areattached to the electrolytic cell are mechanically attached by physicaldeformations to eliminate all soldering and welding steps. This is adistinct advantage since soldering and welding operations are costly anddifficult to produce and the mechanical assembly is much simpler andmore reliable.

The present invention is also directed to improvements in electrolyticcells of the type shown in the Mintz copending application whereinmultiple-electrode structures are included within the electrolytic cell.Generally,

- the present invention is directed to the use of multiple innerelectrodes which are concentric with the outer electrode structure. Themultiple inner electrodes may extend from opposite ends of the outerelectrode member or may extend from the same end of the outer electrodemember.

One embodiment of the present invention, for example, includes aconcentric multiple inner electrode structure which extends from theopen end of the outer electrode and is concentric within the outerelectrode. Another embodiment of the present invention includes an innerelectrode which extends within a recess in the closed end of the outerelectrode structure. The recess may be produced by folding in the closedend of the outer electrode. The recess may be completely separate fromthe main internal chamber of the outer electrode or the recess mayinclude an opening so as to provide for communication between the recessand the main internal chamber of the outer electrode.

The use of a folded-in structure so as to provide a recess for an innerelectrode may be also used so as to provide an attachment point for anelectrical lead. For example, a smaller recess may be formed in theclosed end of the outer electrode and a flange portion of an electricallead disposed within the recess. The outer ends of the recess may thenbe folded in so as to support the flange portion within the recess andso as to provide for a mechanical maintenance of the electrical lead ingood physical contact with the outer electrode.

The present invention is, therefore, directed to improvements inelectrolytic cells and specifically is directed to improvements inelectrolytic cells of the type wherein one electrode serves as an outerhousing. The improvements of the present invention are directed to the'use of multiple inner electrodes for the electrolytic cell so as toprovide for more than one timing function from the electrolytic cell andto new structures for attaching electrical leads to the electrolyticcell so as to eliminate the costly soldering or welding operations.

A clearer understanding of the invention will be had with reference tothe drawings, wherein:

FIGURE 1 is a cross section of a first embodiment of the invention usinga concentric multiple inner electrode structure;

FIGURE 2 is a fragmentary view of the inner portion of the innerelectrode of FIGURE 1 prior to physical deformation;

FIGURE 3 is a fragmentary view of the outer portion of the innerelectrode of FIGURE 1 prior to physical deformation;

FIGURE 4 is a cross section of a second embodiment of the inventionillustrating the attachment of electrical leads using mechanicaldeformation;

FIGURE 5 is a fragmentary view of a portion of the embodiment of FIGURE4 showing the closed end of the outer electrode prior to physicaldeformation;

FIGURE 6 is a fragmentary view of a portion of the embodiment of FIGURE4 showing the attachment of the electrical lead to the inner electrode;

FIGURE 7 is a cross-section of a third embodiment of the inventionshowing a triple concentric inner electrode;

FIGURE 8 is a cross-section of a fourth embodiment of the inventionhaving inner electrodes extending from both ends of the outer electrode;

FIGURE 9 is a fragmentary view of a portion of the embodiment of FIGURE8 showing the recessed portion in the closed end of the outer electrodeprior to physical deformation;

FIGURE 10 is a cross-section of a fifth embodiment of the presentinvention having a first inner electrode extending into a recess formedin the closed end of the outer electrode and a dual inner electrodestructure extending into the open end of the outer electrode; and

FIGURE 11 is a fragmentary view of the dual inner electrode of FIGURE 10illustrating the outer portion of the dual electrode prior to physicaldeformation.

In FIGURE 1, a first embodiment of an electrolytic cell in accordancewith the invention is shown and the first embodiment includes an outerhousing 10 which serves as an outer electrode. The outer housing has amajor axis. The outer electrode 10 has an open and a closed end and maybe constructed of an active material such as silver, or may beconstructed of a base material which includes a coating of the activematerial. The outer electrode includes an enlarged section 12 at theopen end. An electrolyte 14 is contained within the outer electrode 10.The electrolyte may have an appropriate chemical composition and as anexample, when the active material is silver, the electrolyte may becomposed of silver phosphate in a solution of phosphoric acid asdisclosed in copending application Ser. No. 554,003 filed May 31, 1966,in the name of Edmund A, Miller and assigned to the same assignee as theinstant application. As will be seen, the electrolyte contains a mobileionic component of the active metal such as silver.

The inner electrode structure of the embodiment of FIGURE 1 is composedof a pair of concentric electrodes which are disposed substantially onthe major axis of the outer electrode. The concentric electrodes includea first inner electrode 16 which has an outer flange member 18. Theflange 18 fits within the enlarged portion 12 of the outer electrode 10.A pair of insulating members 20 and 22 sandwich the flange within theenlarged portion. Both insulating members are composed of inert plasticmaterial so as not to be contaminated by the electrolyte 14. Theinsulating member 20 is usually composed of plastic material which isrelatively hard since the insulating member 20 must provide support forthe flange 18 within the enlarged portion 12. For example, theinsulating member 20 may be composed of polytetrafluoroethylene which issold under the trade name Teflon by the Du Pont Company.

The second insulating member 22 is composed of plastic material which isrelatively soft since the insulating member 22 is used to provide a sealat the open end of the outer electrode 12. For example, the insulatingmember 22 may be composed of a material such aspolychlorotrifiuoroethylene sold under the trade name KEL-F by MinnesotaMining and Manufacturing Co. The outer edge of the enlarged portion 12is crimped over as shown at position 24 to grip the insulating member 22so as to provide for a tight seal at the open end of the electrolyticcell. The electrolytic cell structure described above with reference toFIGURE 1 is similar to the electrolytic cell shown in the Mintz andMiller copending applications. The electrolytic cell of the presentinvention, however, provides for an additional inner electrodeconcentric with the first inner electrode 16.

The first inner electrode 16 is tubular and includes enlarged innerportions 26 and 28. A second inner electrode 30 is designed to fitconcentrically within the first inner electrode 16. The second innerelectrode 30 includes a flange portion 32 to fit within the enlargedinner portion 26. A pair of insulating members 34 and 36 sandwich theflange portion 32 within the enlarged portion 26. A third insulatingmember 38 fits over the second inner electrode 30 and the insulatingmember 38 fits within the enlarged inner portion 28 of the first innerelectrode 16.

A tip portion 40 of the first inner electrode 16 is physically deformedor crimped so as to grip the insulating member 36 and seal the secondinner electrode 30 within the first inner electrode 16. An end portion42 of the first inner electrode 16 may be crimped inward so as to gripthe insulating member 38 thereby mechanically securing the second innerelectrode 30 within the first inner electrode 16. As can be seen inFIGURE 1 the seal at the inner portion of the dual inner electrodestnucture is formed by the insulating members 36 and 34 and the flange32 and the seal is similar to the seal at the end of the outer electrodewhich is formed by the insulating members 20 and 22 and the flange 18.The insulating members 34 and 36 may be composed of materials which aresimilar to the insulating members 20 and 22. For example, insulatingmember 34 may be composed of Teflon and insulating members 36 and 38 maybe composed of KEL-F.

FIGURES 2 and 3 show fragmentary views of the inner and outer portionsof the dual inner electrode structure of FIGURE 1 prior to the physicaldeformation of the end portions. In FIGURE 2 it can be seen that the tipportion 40 is initially straight so that the sandwich constructionincluding the pair of insulating members 34 and 36 surrounding theflange 32 may he slid into the enlarged inner structure 26. At the otherend of the dual inner electrode structure, as shown in FIGURE 3, theinsulating member 38 is slid over the second inner electrode 30 and intothe enlarged portion 28. The dual electrode structure is then sealed bycrimping over the tip portions 40 and 42 so as to physically secure thesecond inner electrode 30 within the first inner electrode 16. The innerelectrodes 16 and 36 are also insulated from each other due to the useof insulating members 34, 36 and 38.

The inner electrodes of the present invention usually include a maskinglayer of inert material which serves as a plating surface for the activematerial. This inert material is electrochemically non-reactive with theelectrolyte. The active material may be plated onto the layer of inertmaterial of the inner electrodes during a first particular type ofoperation of the electrolytic cell. Specifically, the mobile ioniccomponents of the active metal such as silver are selectivelyelectroplatable on and deplatable from the masking layers on the innerelectrodes. As a second particular type of operation of the electrolyticcell, the active material may be pre-plated on the inner electrodes andthe electrolytic cell is operated by deplating the active material fromthe inner electrodes to the outer electrode. The pre-plating of theactive material, therefore, operates as a predetermined timing functionwhich is built into the electrolytic cell prior to the use of theelectrolytic cell.

One particular material which may be used for the inert layer ofmaterial to receive the active material is gold. Since gold isrelatively expensive, the electrodes are usually constructed of a basematerial such as steel, which is then plated with the gold. For example,the plating may be in accordance with the plating process described inco-pending application Ser. No. 576,601 filed on Sept. 1, 1966, in thenames of Martin Mintz and Leon P. Brown and assigned to the sameassignee as the instant case. Because of the particular structure of thepresent invention the plating operation may actually be accomplished intwo steps. For example the inner electrodes 16 and 30 may be initiallyplated prior to assembly so that the inner electrodes both have acoating of inert material. The dual inner electrode structure is thenassembled using the various insulating members described above and thetip portions 40 and 42 crimped into position. The dual inner electrodestructure may then be subject to a final plating operation to depositthe proper amount of inert material such as gold. The dual platingoperation is preferable to a single plating operation since it insuresthat all areas of the electrode structure are coated with inert materialwhich eliminates corrosion which might occur due to a slight mechanicalfailure within the inner electrode structure.

The embodiment of FIGURE 1 also includes a pair of lead members 44 and46 which are attached to the outer electrode 12 and the first innerelectrode 16. The usual method of attaching the lead members 44 and 46is by soldering or welding. The inner electrode 30 may also have a leadmember Welded to provide an extension or the inner electrode 30 may bemade sufficiently long so as to act as its own electrical lead. Theattachment of electrical leads by such as soldering or welding arerelatively expensive and the attachment is difficult to perform withgreat reliability. It would therefore be desirable to attach theelectrical leads such as the electrical leads 44 and 46 with amechanical method of attachment which may be automated for greaterreliability and lower cost.

FIGURE 4 illustrates a second embodiment of the invention generallysimilar to the embodiment of FIG- URE 1 but including electrical leadswhich are connected by a mechanical method of attachment. Similarelements in FIGURE 4 are given the same reference character fromFIGURE 1. In the embodiment of FIGURE 4, the outer electrode includesthe enlarged portion 12 and the dual inner electrode structure includinginner electrodes 16 and 30 is sealed at the open end of the outerelectrode 10. The dual inner electrode is sealed through the use of theinsulating members 20 and 22 sandwiching the flange 18 within theenclosed portion 12. The

inner electrode 30 is sealed within the inner electrode 16 by the use ofthe insulating members 34, 36 and 38.

The outer electrode 10 is folded in at its closed end to form a recess.This may be more clearly shown in FIGURE 5 where the folded end of theouter electrode 10 is designated by reference character 50. The recesswhich is formed at the closed end 50 is designated by referencecharacter 52. As can be seen in FIGURES 4 and 5, an outer lead 54includes a flange member 56 and the flange member is disposed within therecess 52 and up against an end wall 58 of the recess 52. FIGURE 5 showsthe electrical lead 54 in position within the recess 52 prior to thephysical deformation of the end portion 50 of the outer electrode 10.FIGURE 4 illustrates the end portion 50 physically deformed or crimpedso as to securely maintain the flange 56 up against the end wall 58. AScan be seen in FIGURES 4 and 5, the electrical lead 54 is securelymechanically attached to the outer electrode 10 to thereby provide agood electrical connection between the electrical lead 54 and the outerelectrode 10.

The embodiment of FIGURE 4 also includes an electrical lead 60 forattachment to the inner electrode 16 which does not require anysoldering or welding. The electrical lead 60 includes a circular bandportion 62. The band portion 62 circumferentially surrounds the innerelectrode 16 and the band portion 62 is maintained in position by aseries of crimps 64 which physically deform the band portion and theinner electrode 60 as shown in FIGURE 4. FIGURE 6 illustrates the bandportion 62 surrounding the inner electrode 16 and in FIGURE 6 the crimps64 can be seen to extend completely around the circumference of the band62. The electrical lead assembly shown in FIGURE 6 may be mechanicallyattached to the inner electrode assembly at a time prior to the finalplating of the inner electrode assembly. Therefore, when the innerelectrode assembly is finally plated, the lead member 60 is not onlymechanically attached by the crimps 64 along the band 62 but the platingitself provides for an attachment of the lead 60 to the inner electrode16.

FIGURE 7 illustrates a third embodiment of the invention which includesa triple concentric inner electrode. The embodiment of FIGURE 7 issimilar to the embodiment of FIGURES 1 and 4 in that all the innerelectrodes are concentric to each other. In FIGURE 7 an outer electrodehas an enlarged section 102. The series of three inner electrodes areconcentric with each other and include a first inner electrode 104, asecond inner electrode 106 and a third inner electrode 108. Theelectrode 104 includes a flange portion 110 to fit within the enlargedsection 102 of the outer electrode 100. The flange portion 110 issandwiched by two insulating members 112 and 114 which may be similar tothe insulating members 20 and 22 of FIGURE 1. The open end of the outerelectrode 100 is crimped over so as to seal the electrolytic cell.

The inner electrode 104 includes a pair of enlarged inner portions 116and 118 at each end. The inner electrode 106 includes a flange member120 to fit within the enlarged portion 116. The flange portion 120 isflanked by a pair of insulating members 122 and 124 which are similar tothe insulating members 32 and 36 of FIGURE 1. A tip portion of theinsulating member 104 is crimped into the insulating member 124 so as toprovide a seal. An insulating member 126 is disposed within the enlargedportion 118, and the other end of the inner electrode 104 is crimped into provide a seal between the inner electrode 104 and the innerelectrode 106.

Finally, the inner electrode 106 includes a pair of enlarged innerportions 128 and 130. The inside inner electrode 108 includes a flangeportion 132 to fit within the enlarged inner portion 128. A pair ofinsulating members 134 and 136 similar to the insulating members 34 and36 of FIGURE 1 sandwich the flange portion 132 within the enlargedportion 128. A tip portion of the inner electrode 106 is crimped toprovide a seal between the inner electrode 106 and the inner electrode108 within the outer electrode 100. An insulating member 138 is disposedin the enlarged portion 130 and the end of the inner electrode 106 iscrimped into the insulating member 138 so as to provide a seal betweenthe electrodes 106 and 108 outside the outer electrode 100. The outerelectrode contains an electrolyte 138.

As can be seen in FIGURE 7, all of the insulating members and flangeportions are similar to those shown in FIGURE 1, but the embodiment ofFIGURE 7 has a triple concentric inner electrode. A lead member 140 isattached to the outer electrode 100 by soldering of a flange portion 142to the outer electrode 100. It is to be appreciated that the lead member140 may be attached in a manner similar to that shown in FIGURE 4 byfolding in the closed end of the outer electrode 100 to form a recess.In addition, lead members 144 and 146 are attached to the innerelectrodes 106 and 104 by some appropriate means such as soldering orwelding. Again, it is to be appreciated that these lead members may beattached by a physical deformation using a lead structure as shown inFIGURES 4 and 6.

FIGURE 8 shows a fourth embodiment of the invention wherein a pair ofinner electrodes are concentric with an outer electrode and the innerelectrodes extend into the outer electrode from opposite sides.Specifically the embodiment of FIGURE 8 may use an electrolytic cell asshown in the copending Mintz application Ser. No. 519,634 and whereinthe electrolytic cell has the closed end of the outer electrode foldedin to receive a second inner electrode. As shown in FIGURE 8, an outerelectrode 200 has an enlarged section 202 at the open end of the outerelectrode and a folded-in section 204 at the closed end of the outerelectrode. A first inner electrode 206 including a flange portion 208 isinserted into the outer electrode 200 at the open end.

A pair of insulating members 210 and 212 sandwich the flange portion 208within the enlarged section 202 and the insulating members may be of thesame type used in FIGURE 1. For example, insulating member 210 may becomposed of Teflon and insulating member 212 may be composed of KrEL-F.The open end of the outer electrode 200 is crimped in so as to grip theinsulating member 212 and so as to provide a seal between the innerelectrode 206 and the outer electrode 200. It is to be appreciated thatthe inner electrode may be plated with an inert material such as gold,as may all of the inner electrodes described in this application. Also alead member 214 may be attached to the inner electrode 206.

The closed end of the outer electrode 200 has the folded-in section 204as described above. The folded-in portion 204 encloses a recess 216which is designed to receive an electrode. An electrode 218, which hasan integral flange portion 220, extends into the recess 216. A pair ofinsulating members 222 and 224 sandwich the flange portion 220 withinthe recess and against an inner wall portion 226. An insulating member229, composed of hard material is positioned adjacent to the insulatingmember 224. The recess and the main chamber portion of the outerelectrode are both filled with an electrolyte 230.

A seal is produced between the inner electrode 218 and the outerelectrode 200 by physically deforming end portions 228 so as to grip theinsulating member 229. FIGURE 9 shows the end portions 228 before theyare physically deformed and it can be seen that flange portion 220 ofthe inner electrode 218 is merely inserted into the recess 216 after theinsulating member 222 has been placed in the recess 216 and theinsulating members 224 and 229 are then slid over the electrode 218. Thefinal seal is accomplished by physically deforming the end portions 228.It is to be appreciated that the inner electrode 218 just as all of theother inner electrodes disclosed in this application may be plated withgold or other inert material in a manner provided for in the Mintz andBrown copending application Ser. No. 576,601.

It may also be seen that the embodiment of FIGURE 8 may be easilyadapted from the electrolytic cell disclosed in the Mintz copendingapplication Ser. No. 519,634 so as to produce a dual electrodeelectrolytic cell. A lead member 232 may be attached to the outerelectrode 200 to complete the dual electrolytic cell.

FIGURE 10 shows a fifth embodiment of the invention which is amodification of the embodiment of FIGURE 9 but additionally including amodified dual inner electrode similar to that shown in FIGURES 1 and 4.In FIGURE 10 an outer electrode 300 includes an enlarged section 302 anda folded-in portion 304. The folded-in portion contains a first innerelectrode 306 which has an integral flange portion 308 sandwichedbetween a pair of insulating members 310 and 312 and including anadditional hard material insulating member 313. The electrode 306 andsurrounding structure is essentially similar to that shown in FIGURE 9except an opening 314 communicates between a recess 316 and a mainchamber 318 within the outer electrode 300. The opening 314 may be usedso as to insert the electrolyte within the electrolytic cell in oneoperation or the opening 314 may be used to help eliminate bubbles whichmay be trapped within the electrolytic cell. A lead member 319 may beattached to the outer electrode 300.

The electrolytic cell of FIGURE 10 also includes a dual inner electrodedisposed within the open end of the outer electrode 300. The dual innerelectrode includes a first inner electrode 320 and a second innerelectrode 322. The first inner electrode includes an integral flangeportion 324 and the second inner electrode includes an integral flangeportion 326. The flange portion 324 is sandwiched within the enlargedsection 302 of the outer electrode 300 by a pair of insulating members328 and 330. The first inner electrode 320 is maintained in sealedengagement by the crimp provided at the open end of the outer electrode300 and this structure is essentially similar to that shown in FIGURES1, 4, 7 and 8.

The inner electrode 320 also includes an enlarged inner portion 332. Theinner electrode 322 includes the integral flange 326 within the enlargedinner portion 332 and the flange 326 is sandwiched by a pair ofinsulating members 334 and 336. The insulating members 334 and 336provide for a seal between the inner electrodes 320 and 322 by aphysical deformation of a tip portion 338 so as to gripthe insulatingmember 336. As discussed above, the insulating members may be of thetype discussed with reference to FIGURES 1, 4, 7 and 8 and specificallyinsulating member 334 may be composed of Teflon and insulating member336 may be composed of KEL-F. The remaining open area between electrodes.320 and 322 is filled by an insulating sleeve member 340. The sleevemember 340 provides for complete insulation between the electrodes 320and 322 and eliminates any possibility of shorting between theelectrodes. The outer tip portion 342 may be crimped inward so as toprovide for a mechanical gripping of the insulating sleeve 340. FIGURE11 illustrates the embodiment of FIGURE 10 wherein the tip portion 342has not been physically deformed.

As can be seen by the above disclosure, the present invention isdirected to improvements in electrolytic cells. Specifically, thepresent invention provides for inner electrode structures which aremultiple electrodes so that the electrolytic cell of the presentinvention may provide more than a single timing or integration function.In addition, the electrolytic cells of the present invention include themechanical attachment of eelctrica-l leads as to eliminate all solderingor welding operations.

The present invention has been illustrated by many embodiments showingvarious alternative structures. Generally, the various seals betweenelectrodes is accomplished using a sandwich structure incorporating ametal flange and a pair of insulating members. It is also to be notedthat in all of the examples given, the outer electrode or housing isusually constructed of an active material, for example, silver, and theinner electrodes all include a layer of inert material, for example,gold. In addition an electrolyte is always present between theelectrodes. Also, the inner electrodes of the present invention may beplated with predetermined amounts of active material and this activematerial may be then transferred to the outer electrode so as to providefor a predetermined timing operattion.

The physical construction of the present invention includes a concentricrelationship nature between the inner electrodes and the outerelectrode. In addition some embodiments of the present invention includea concentric relationship between multiple inner electrodes. Also, thephysical constructions of the present invention may encompass thefolding-in of the outer conductor to form a recess to either receive anelectrical lead or an inner electrode. The present invention alsoprovides structures for mechanically attaching electrical leads withoutsoldering or welding.

It should be noted that the embodiments shown in FIG- URES 9 and 10 donot disc-lose electrical leads for the outer electrode, but it is to beappreciated that such electrical leads may be attached by crimping.soldering or welding as illustrated by other embodiments of theinvention. The present invention has been illustrated with relation toparticular embodiments and specific structures but it is to beappreciated that various adaptations and modifications may be made. Theinvention is, therefore, only to be limited by the appended claims.

What is claimed is:

1. An electrolytic cell in combination, comprising an opencontainer-electrode having a metal inner surface and a major axis,

an electrolyte containing a mobile ionic component of and contactingsaid metal surface,

a first electrode within said container-electrode, disposedsubstantially on the major axis and spaced from said inner surface andhaving an electrically conductive masking layer on its surface incontact and chemically non-reactive wit-h said electrolyte, said mobileionic component being selectively electroplatable on and deplatable fromsaid masking layer,

a second electrode within said container-electrode, disposedsubstantially on the major axis and spaced from said inner surface andfrom the first electrode and having an electrically conductive maskinglayer on its surface in contact and chemically non-reactive with saidelectrolyte, said mobile ionic component being selectivelyelectroplatable on and deplatable from the masking layer on said secondelectrode, and

first and second discrete electrically insulative means for supportingsaid electrodes respectively in and sealingly closing saidcontainer-electrode.

2. The electrolytic cell set forth in claim 1 comprising the firstelectrode disposed within the container-electrode at a first end of thecontainer-electrode and the second electrode disposed at a second end ofthe container-electrode opposite to the first end and the secondelectrically insulative means sealing the second electrode with thecontainer-electrode.

3. The electrolytic cell set forth in claim 1 comprising the first andsecond electrodes disposed within the container-electrode at one end ofthe container-electrode and the second electrode disposed within thefirst electrode and the second electrically insulative means sealing thesecond electrode support with that of the first electrode.

4. An electrolytic cell in combination, comprising an opencontainer-electrode with a wall and having a major axis,

an electrolyte contacting a wall of said container electrode,

a first electrode dis-posed substantially on the major axis within anopening in said container-electrode and having a first outer surfacespaced from the wall of the container-electrode and contacting theelectrolyte,

a second electrode disposed substantially on the major axis and having asecond outer surface spaced from the first electrode and the wall of thecontainerelectrode and contacting the electrolyte,

at least one wall of the container-electrode and said first and secondouter surfaces comprising a masking layer electrically conductive andchemically nonreactive with said electrolyte, and at least another oneof the container-electrode and the first and second outer surfaces beingof metal,

the electrolyte containing a mobile ionic component of said metal, saidmobile ionic component being selectively electroplatable on anddeplatable from said chemically non-reactive masking layer,

first electrically insulative means sealing an opening of thecontainer-electrode and supporting said first electrode projectingtherefrom into the containerelectrode, and

second electrically insulative means sealing the second electrode withone of said first electrode or said container-electrode.

5. The electrolytic cell set forth in claim 4 comprising the first andsecond electrodes respectively extending substantially on the major axisfrom opposite ends of the container-electrode and the secondelectrically insulative means sealing the second electrode support withthe container-electrode.

6. The electrolytic cell set forth in claim 4, comprising:

a third electrode disposed within the container-electrode substantiallyon the major axis and having a third outer surface spaced from the firstand second electrodes and said wall of the container-electrode, thethird outer surface of said third electrode being of material like thatof the outer surface of said first and second electrodes and thirdelectrically insulative means sealing said third electrode support withthat of the second electrode.

7. An electrolytic cell in combination, comprising an opencontainer-electrode with a wall and having a major axis,

an electrolyte contacting a wall of said containerelectrode,

a first electrode disposed substantially on the major axis within anopening in said container-electrode and having a first outer surfacespaced from the wall of the container-electrode and contacting theelectrolyte,

a second electrode disposed substantially on the major axis and having asecond outer surface spaced from the first electrode and the wall of thecontainer electrode and contacting the electrolyte,

at least one wall of the container-electrode and said first and secondouter surfaces being electrically conductive and chemically non-reactivewith said electrolyte, and at least another one of thecontainerelectrode and the first and second outer surfaces being ofmetal,

the first and second electrodes respectively extending into thecontainer substantially on the major axis through one opening in thecontainer,

the electrolyte containing a mobile ionic component of said metal, saidmobile ionic component being selectively electroplatable on anddeplatable from said chemically nonreactive masking surface,

first electrically insulative means sealing the opening of thecontainer-electrode and supporting said first electrode projectingtherefrom into the containerelectrode, and

second electrically insulative means sealing the second electrodesupport with that of a first electrode.

8. An electrolytic cell in combination, comprising an electrolytecontaining a mobile ionic component of a metal,

three electrodes electrically insulated from each other and in contactwith the electrolyte, one of said electrodes having a surface of themetal, the metal being electrochemically active with said electrolyte,another one of said electrodes having an electrically conductive maskinglayer in contact with and chemically non-reactive with said electrolyte,and said mobile ionic component being selectively electroplatable on anddeplatable from said masking layer, one of said electrodes being asealed container holding said electrolyte, the other two electrodesbeing substantially on the major axis of said container, and first andsecond discrete electrically insulativc means for supporting saidelectrode respectively in and sealingly closing saidcontainer-electrode.

9. The electrolytic cell set forth in claim 38 comprising said other twoelectrodes respectively extending substantially on the major axis fromopposite ends of the sealed container and means electrically insulatingand sealing the other two electrodes projecting through the wall of theelectrode constituting the sealed container.

10. An electrolytic cell in combination, comprising an electrolytecontaining a mobile ionic component of a metal,

three electrodes electrically insulated from each other and in contactwith the electrolyte, one of said electrodes having a surface of themetal, the metal being electrochemically active with said electrolyte,another one of said electrodes having an electrically conductive maskingsurface in contact with and chemically non-reactive with saidelectrolyte, and said mobile ionic component being selectivelyelectroplatable on and deplatable from said masking surface, one of saidelectrodes being a sealed container holding said electrolyte, the othertwo electrodes being substantially on the major axis of said container,the other two electrodes extending into the sealed container from thesame end of the container and one of the other two electrodes beingdisposed Within the other of the two electrodes, and

first and second electrically insulative means for electricallyinsulating and sealing the other two electrodes relative to each otherand the sealed container.

11. An electrolytic cell, including,

a container-electrode having a major axis and a wall,

a first electrode disposed within said container-electrode on an axissubstantially parallel to said major axis and including a first surfaceand a flange portion,

a second electrode disposed within said containerelectrode on an axissubstantially parallel to said major axis and including a second surfaceand a flange portion,

an electrolyte within said container-electrode in contact with saidsurfaces of the first and second electrodes and the wall of thecontainer-electrode,

at least a first one of a section of the wall of thecontainer-electrode, said first and said second surfaces having firstelectrically conductive means for providing electro-chemical transfer ofmobile ionic components of said first electrically conductive means tosaid electrolyte and at least a second one of a section of the Wall ofthe container electrode, said first and said second outer surfaceshaving a second electrically conductive means for preventingelectrochemical transfer of mobile ionic components of said secondelectrically conductive means to said electrolyte,

first insulating means in the wall of the containerelectrode and againstthe flange portion of the first electrode for electrically insulatingand hermetically sealing the first electrode within thecontainer-electrode, and

second insulating means in the wall of the containerelectrode disposedagainst the flange portion of the second electrode for electricallyinsulating and hermetically sealing the second electrode within thecontainer-electrode.

12. The electrolytic cell set forth in claim 11,

comprising the outer member being enlarged at the end receiving thefirst inner electrode and the first insulating means including first andsecond insulating members disposed in the enlarged end of the outerelectrode on opposite sides of the flange on the first inner member andthe outer edge of the enlarged end of the outer electrode being crimpedover against one of the first and second insulating members. 13. Theelectrolytic cell set forth in claim 12,

comprising ing the first and second inner electrodes respectivelyextending from the outer electrode through the enlarged end of the outerstructure and the end opposite to the enlarged end and the secondinsulating means including third and fourth insulating members disposedon opposite sides of the flange on the second inner electrode and theouter electrode gripping at least one of the third and fourth insulatingmembers.

15. The electrolytic cell set forth in claim 14,

comprising the outer electrode being closed at the end opposite to theenlarged end and being recessed and the flange on the second innerelectrode being disposed in the recess and the third insulating memberbeing disposed in the recess between the closed end of the outerelectrode and the flange on the second inner member and the outerelectrode being crimped against the fourth insulating member and thethird insulating member being hollow and the electrolyte being disposedwithin the hollow portion of the third insulating member.

16. In an electrolytic cell,

a first electrode having a closed end folded on itself defining a recesshaving an end wall, said first electrode having a major axis and asurface,

a second electrode disposed substantially on the major axis within saidrecess and having a flange with a surface facing the surface of thefirst electrode,

first insulating means disposed Within the recess between the surface ofthe first electrode at the closed end thereof and the surface on theflange of the second electrode and having a hollow configuration,

an electrolyte in the hollow portion of the first insulating means andin contact with said surface respectively of the first and secondelectrodes,

one of said first and second surfaces being electrically conductive andchemically non-reactive with said electrolyte and the other of saidfirst and second surfaces being a metal,

said electrolyte containing a mobile ionic component of said metal, themobile ionic component being selectively electroplatable on anddeplatable from said chemically non-reactive surface, and

second insulating means disposed against the oppos' surface of saidflange.

17. In the electrolytic cell set forth in claim 16,

the first electrode being crimped at the folded portion to seal thesecond insulating means against the first and second electrodes.

18. An electrolytic cell in combination, comprising acontainer-electrode With an opening and an inner surface,

an electrolyte in said container-electrode,

-a first electrode disposed Within the opening in thecontainer-electrode and having a first outer surface spaced from theWalls of the container-electrode and having a hollow configuration,

a second electrode disposed within the opening in thecontainer-electrode and Within the hollow configuration of the firstelectrode and having a second outer surface spaced from the walls of thecontainerelectrode and from the first electrode,

at least one of said Wall of the container-electrode, said first andsaid second outer surfaces being electrically conductive and chemicallynon-reactive with the electrolyte, and at least another one of said Wallof the container-electrode, said first and said second outer surfacesbeing a metal,

said electrolyte containing a mobile ionic component of said metal, saidmobile ionic component being selectively electroplatable on anddeplatable from said chemically non-reactive surface,

first insulating means sealing the opening of the container-electrodeand supporting said first electrode projecting therefrom into thecontainer-electrode, and

second electrically insulative means sealing the second electrode in thefirst electrode.

19. The electrolytic cell set forth in claim 18,

comprising first electrode and the second electrode having a flange andthe second insulating means comprising third and fourth insulatingmembers disposed between the first and second electrodes and sandwichingthe second flange and the first electrode gripping at least one of thethird and fourth insulating members against the second electrode.

20. The electrolytic cell set forth in claim 19,

comprising References Cited UNITED STATES PATENTS 858,574 7/1907Churcher 317-233 2,154,026 4/1939 Brennan 317-230 2,736,846 2/1956Gables 3l7230 2,739,275 3/195 6 Houtz et al. 31723O 2,791,473 5/1957Mattox 3172 31 X 3,017,612 1/1962 Singer 317231 3,119,754 1/1964Blumenfeld et al. 324-68 3,125,673 3/1964 Puterbaugh 235-92 3,158,79811/1964 Sauder 317231 X 3,172,083 3/1965 Constatine 340-173 3,210,66210/ 1965 Steinmetz et al. 324-94 3,346,783 10/1967 Millard 317--23OFOREIGN PATENTS 1,921,265 8/1965 Germany.

JAMES D. KALLAM, Primary Examiner.

US. Cl. X.R.

